Treating cellulose derivative materials



Fatented 1 mama PATENr or ca Joseph B. Dickey nudism G. McNally, Rochassis'nors to Eastman Kodak Company, Rochester, N. Y.,,a corporation .of New Jersey No Drawing.

7 Claims.

This invention relates to the conditioning of textile yarns and more particularly to the conditioning of filaments and yarns composed. of organic derivatives of cellulose such as cellulose g acetate, cellulose propionate, cellulose acetate propionate, and cellulose acetate butyrate, to render them more amenable to textile operations such as knitting and the like. This invention also relates to compositions of matter in which it cellulose derivatives, such as cellulose acetate, cellulose'nitrate or cellulose ethers, are combined or mixed with other substances, such as a compatible plasticizer, and a common solvent for both, with or without other useful addition i agents, so that the resulting product will have properties such as will make the composition highly advantageous for use in the plastic and analogous arts, such for instance, as the manufacture of wrapping sheets, photographic film, sowartiflcial silk, varnishes or lacquers, and the like. As is well known-in the manufacture of yarns, particularly those composed of orv containing cellulose organic derivatives, it is necessary to treat the yarn in order to reduce the tendency towardbreae of the individual filaments or iibers when they are subjected to various mechanical strains and to lubricate the yarn in order to facilitate handling in such operations as spinning, twisting, winding and reeling. It is also necessary totreat yam to adapt it for use as warp or filling or for the manufacture of various types of knitted fabrics. In mitting, it is particularly important that the yarn. be soft and pliable in order that it may conform readily to the contour of the needles and thus produce a closely knit fabric free from such defects as stitch distortion", pin holes, laddering, and the like.

Heretofore it has been proposed to employ softening agents such as polyhydric alcohols and similar agents as ingredients of yarn conditioning or lubricating formulas, generally in connection with mineral, animal or vegetable oils. It has been found, however, that most of the known softening agents and the various formulas containing them have certain drawbacks, one of the most serious of which is higl'rvapor pressure, and

'- in some cases too drastic a solvent action on the yarn. Many of such agents possess slight or,

insuflicient solvent power for the lubricants with which they are used, and it is accordingly necessary to employ "blending agents or emulsifyingagents in order to obtain operable yarn treating formulas. In addition, many of the known softening and lubricating agents are insumciently Application December 17, 1938, Serial No. 246,51!

soluble in water to permit satisfactory removal by aqueous scour baths.

While in the plastic and related arts cellulose acetates, nitrates and others have been known for decades, it has also been known that to utilize them it is necessary to mix therewith such plasticizing or conditioning agents as camphor, castor oil, triphenyl phosphate, monochlornaphthalene or the like. Certain of these and other addition agents are also added for the purpose of reducing the inflammability of the product. Plastic inducing agents, such as the higher alcohols and their esters, are sometimes also added. Similarly, addition compounds of various kinds have been employed to increase flexibility, transparency, toughness, and other properties which will enhance the value of the resulting product. Addition products for the same or similar purposes are also added to cellulose acetates, nitrates and ethers to prepare them for use in the other plastic arts, such as in the manufacture of lacquers, varnishes, artificial silk filaments, moulded compounds and the like. While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to which cellulose derivatives have been put and the increasing number of desirable properties required of the cellulose derivative for most purposes has made the discovery of new and economical plasticizers or other ,addition agents a matter of considerable importance to the art.

This invention has as its principal object to provide an entirely new class of yarn conditioning agents which are particularly adapted for the treatment of yarns composed of 01 containing organic derivatives of cellulose and capable of lubricating, softening and rendering such yarns larly those composed of or containing organic derivatives of cellulose such as cellulose acetate, whereby the yarn is rendered soft and pliable and capable of employment in a variety of textile operations where complicated designs or stitches are employed. Another object is to provide an, 1 improved type of yarn which is especially amenable to textile operations including circular knitting, weaving, spinning and the like. son another object of this invention is to produce a composition 01' matter which may be made into permanently transparent, strong and flexible.

sheets or films of desired,thi.nness which are substantially waterproof, are unaffected by ordinary photographic fluids and possess the desired properties of a support for sensitive photographic coatings. Yet another object of our invention is to produce a. composition which is capable of easy and convenient manipulation in the plastic and analogous arts, such as in the manufacture of sheets, films, artificial silk filaments, varnishes, lacquers and the like, and to produce a composition which'will not injure, or be injured by, the substances or surfaces with which it is associated during manufacture. Other objects will appear hereinafter.

These objects are accomplished by the following invention which, in its broader aspects, comprises the discovery that esters of hydroxyalkoxy tetrahydrofurfuryl ethers having the general formula:

where n is a small whole number at least one; a: is a small whole number at least one; B is a substituent selected from the group consisting of hydrogen, alkyl and hydroxy alkyl groups, and R is a substituent selected from the group consisting of the alkyl, cycloalkyl, aryl and heterocyclic groups, may be used as yarn conditioning agents and particularly as softening agents, with or without the addition of animal, mineral, or vegetable oils, in the treatment of yarns comcellulose. We have found that these compounds when employed as described in the detailed examples set forth below have a slight solvent and/or softening action on cellulose organic derivative yarns which renders such yarns soft and pliable without at the same time having too drastic-an action thereon.

These compounds are prepared by treating hydroxyalkoxy tetrahydrofurfuryl ethers, which have the general formula with acids, acid anhydrides and acid chlorides with or without the presence of a catalyst. These ethers may be prepared in accordance with the process set forth in my copending application Serial No. 246,205, filed December, 16, 1938. When acids are used we may carry out the esterification in the presence of a catalyst such as sulfuric, phosphoric, p-toluene-sulfonic acid posed of or containing organic derivatives of.

and particularly compatible with cellulose acetate in the percentages hereinafter given.

Pan aea-non or Comotmns Tetrahydrofurfurorycthoxuethoryethul acetate 46 gmof triethyiene glycol tetrahydrofurfuryl ether and 30 gm. of acetic anhydride are refluxed for 1 hr. The product is then worked up to give the ester boiling 180-5/0.1 mm.

Tetrahydrofurfuroxyethoxy ethyl butyrate 95 gm. of diethylene glycol tetrahydrofurfuryl ether and 90 gm. of butyric anhydride are heated on the steam bath for 1 hr. and then refluxed 5 minutes. The yellow product is then fractionated. The desired ether ester boils at 180-5/15 mm.

Tetrahydrofurfurozy ethyl tetrahudrolurjurozw acetate 96 gm. of tetrahydrofurfuroxy acetic acid, 100 gm. of tetrahydrofurfuroxy ethanol, 0.3 gm. p-toluene sulfonic acid, and 150 cc. toluene are distilled so that the toluene returns tothe reaction vessel. The theoretical quantity of water is collected during 6 hrs. The productis then washed with 10% sodium carbonate and distilled under vacuum. Toluene and the excess alcohol come off and then the ester, boiling 183-90/3 mm.

Tetrohydrojurfuroxy ethyl succinate 35 gm. of succinic acid, 100 gm. 5 tetrahydrofurfuroxy ethanol, 0.2 g. p-toluene sulfonic acid, and 100 cc. benzene are refluxed in such a manner that the benzene separates from the water 4 formed and returns tothe reaction. After the necessary quantity of water has been collected, the product is washed with sodium carbonate solution (10%). The benzene and excess alcohol are removed and the ester distilled under vacuum. 47 gm. (70%) are obtained, boiling at 225-/3 mm.

The following table gives the constants of some of the compounds claimed in this sketch sheet.

' C. Mm. Tetrahydrofurluroxy ethyl acetate 132-6 20 propionate 138-43 18 succinate- 226-80 3 laumte. 160-75 3 data... 21 0. 1 Tetrahydrofurfnroxy acetate 183-90 3 Tetrahydroiurfuroxy ethoxy ethyl butyrate 180-5 15 acetate 195-210 20 Tetrahydrofurfuroxy ethoxy ethoxy ethyl acetate 180-5 0. 5 butirate 170-5 0. 1 Tetra ydroiuriuryl oxy ethyl tetrahydroiuroat. 150-160 0. 1

TREATMENT or TEXTILE YARNS have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

Our invention will be more readily understood Example 7 moom mo c-cHT- ocm POOQ an by reference to the following examples in which typical applications of the invention are set (fiy m y-fl w y y ur ylether- 1' l'th benzoatc) o I l 23$ todso been il 28 8 1 m q m mn ,1

i3 p-hydroxy ethyl te rahydrofurfuryl e er 0 oleate is applied to textile materials (silk, wool. tfifi 3 m cellulose acetate, cotton, viscose, etc.) by means Example 8 of a wick, roller, spray, bath, pad,-etc., to facilig n. tate their knitting, weaving, spinning and the H-ccH, 8 like. If the yarn is intended primarily for knit JFCHPOOQ'EO 2o ting the amount of conditioning liquid applied v r c may vary from 4-25% by weight of the yarn, and 0 H 0 if the yarn is intended for weaving, the amount (fl-Hydmxy B- w ethyleetmhy v p te) of liquid applied may vary between 15% by Bperm il .00 weight of the yarn.

Example 9 Example 2 He-C-CHa P8113 J} 4 20 cHr-e C- CH=0CgH40C1H -08C H 70 -F=' -3- =O (fi-hydroxy-fl-ethoxy ethyl (ls-meth l) tctrahydrofurggfflfgfgg mhydmmmmm phmxy m fury] ether Blown goyabean oil 60 Olive 01]-- E le 10 and applied to textile materials such as silk, wool, cotton, viscose, cellulose acetate, etc., as described- A 20% solution of cellulose acetate in acetone, in Example 1. If the yarn is intended primarily in which is incorporated 1-25% by weight of the 30 for knitting, the amount of conditioning liquid cellulose acetate of applied may vary from 4-25% by weight or the yarn, and if the yarn is intended for weaving, l the amount of liquid applied'may vary between me 15% by weight of the yarn. Cellulose acetate filaments or fibers treated as described are quite 1,1 i i fifiigifiefititg and mlable gwe Improved ljesults m is extended through orifices into an evaporative various textile operations, such as weaving, knit- 'atmosphere The filaments thus produced are g gf yarn conditioning coinposi wound, or twisted and wound. Yarns, thus prodc r libl llitlf 'tt'. tions which may be applied to various types of u a e p e and s, ab 8 or km mg yarns, particularly those composed of or contain- EaampleII ing cellulose acetate, cellulose acetate propionate, w m P gs 4 cellulose acetate butyrate, and similar cellulose ll f organic acid esters in accordance with our inven- I 4 tion and which render such yarns soft and pliable 10 and especially well adapted for various textile 0 0 p r t s, la y knittin a as follows! weareeutiz iiiilfsi c fflfff? L i fffifff'ff'ffiu 10 Example 3 He-CCH:' Part: omo-om-o-o-cm-c CHn--(OCHrCH:)r-OCCHr-OC"- 4o (fi-hydroxy-B-ethoxy-fi-ethoxy-(5-omega-hydroxy methyl) tetmhydrofuriuryl ethyl ether bis methoxy acetate) Blown olive oil 60 Example 4 H:CCHg CH:CH1

H: C-ZHr-O(C2H4)4O8CsH1s8-0(cz r nr' BS-cg o' O .Q. 20

O (bisw-hydroxy-fl-ethoxy-p-ethoxy-fl-ethoxy tetrahydroiuriuryl ethyl ether) sebacate) Light mineral oil x 80 Example 5 Any of the above compositions may be applied Parts to the yarn intended for use in circular knitting by means of a bath, wick, spray, roller, pad or :0 C C z(0Cz 4)e0 4 v any suitable means. The amount of conditioning o liquid'applied may vary between 5-25% by weight (fi-hydroxy-B-ethoxy-B-ethoxy-fl-ethoxy-fl-ethory of the yarn. Usually,'howeve1: the amount of. mowm m Jfiffliiififiififf'ffii?!.ii'iifi'ifffff? a0 vconditionillg liquid applied is about by weight of the yarn. Yarn composed of cellulose Example 6 acetate conditioned as described above gives excellent results when used in the circular knitting 70 m-c-wm HA(I.'II-CH proceSa H10 -COHQOC2H4O 8C tin 20 As will be apparent from the above examples and description the conditioning agents of our N t, fq-hgdroxy ethyl tetrahydrolurilu'yl other iuroate) invention may be applied-by a wide variety of ea e 0 methods. For example, we may employ the agent i i r i r..-

emulsifying agents, blending agents and the like,

Sill

as an ingredient of the spinningv dope from which the filaments are formed, the amount of the agent so employed depending upon a number of factors, such as the particular cellulose derivative.

It may, for example, be applied to the yarn inside or outside the spinning cabinet, between the guide and godet roll, between the godet or other roll or guide and the point of winding and/or twisting. In some cases, the liquid may even be applied to the yarn after winding onto cones,'spools,

bobbins, or the like or by the so-called bobbin to bobbin method. In the case of staple fiber manufacture, the liquid may be applied to the yarn prior to, or after cutting into staple lengths.

The amount of the agent so employed will vary widely depending upon the results desired, the specific nature of the material to which the agent isapplied, the use to which the yarn is eventually to be put and other factors. For example, in a given case where a cellulose organic acid ester yarn such as a yarn composed of cellulose acetate, is intended for knitting, about 4 to or more by weight, based on the weight of the dry yarn, may be satisfactory, while if the yarn is intended for weaving, the amount may vary between about 1 and 5%.

Although in the above examples we have referred primarily to yarn treating compositions containing only the conditioning agent and an oil, other ingredients such assolvents, non-solvents,

may be added within the. scope of our invention. Likewise, various dyes or other coloring matter may be included in case it is desired to permanently or fugitively tint or dye the material undergoing treatment.

Although we have found it convenient to illustrate our invention by reference to compositions containing specific percentages of the various ingredients, these percentages may vary widely depending upon the particular purpose for which the composition is intended. For example, if it is desired to control the solvent or softening action of the conditioning agent, the amount of the agent may be adjusted as, for example, by redueing the amount of the agent and correspond-, ingly increasing the amount of oil or other inl butyrate, ethyl cellulose, methyl cellulose, benzyl cellulose and others, as well as to the conditioning of silk, wool, cotton, viscose and other natural or artificial materials.

p The term yarn as used herein and in the claims is to be understood as including a single single or multiple threads associated or twisted together, composite threads composed of a mixture of natural and artificial filaments or a composite thread formed by. twisting together individual strands of natural or artificial materials, as well as cut staple fibers produced from natural and/or artificial filaments or threads and spun yarn produced from such staple fibers.

As indicated above, the yarn conditionin agents of our inventionare exceptionally good solvents for a wide variety of mineral, blown and unblown, drying and semi-drying animal and vegetable oils such as cottonseed, olive, cas'tor, neats-foot, sperm and other oils. This enables them to be used with any of such oils in making up a variety of yarn treating formulas of varying composition.

The yarn conditioning method and composi-- tions of our invention possess many outstanding advantages. Thefundamental and outstanding characteristic of the agents employed in accordance with the invention is their ability to soften yarns, especially those composed of or containing organic derivatives of cellulose such .as cellulose acetate and render them soft and pliable and amenable to various textile operations. especially operations such as those involved in weaving and knitting where complicated designs or stitches are employed, without too drastic an action on the yarn material. Another outstanding characteristic of these compounds is their exceptional solvent power for a wide variety of mineral, animal, and vegetable oils and their ability to act as lubricating assistants in conjunction with these oils when applied to such yarns. In addition, due to their solubility in water, they may be readily removed from yarns and fabrics by means of the usual aqueous scour baths. By employing the yarn conditioning agents and method of our invention as herein described, one is enabled to obtain highly satisfactory results in the manufacture of yarns and woven fabrics and especially the production from these yarns of closely knit fabrics free from defects such as pin holes, stitch distortion, laddering and the like.

Us: or COMPOUNDS AS PLASTICIZERS C 0 (Diethylene glycol tetrahydrofurlurylether phthalate) ne -Q Example 13 Cellulose acetate H C CH:

(Diethylene glycol tetrahydroiuriuryl ether adipate) Acetone Methanol Example 14 Cellulose acetate .l

2 (Triethylene glycol tetrahydroiurluryl other succinate) Ethylene chloride 300 Diorane 100 Emmple 1 Parts Cellulose acetate 100 H C OH! CH:-CH

nz (EH-CHr-O CIHr-O C-C' Hg 0 0 0 (fi-Hydrxy. ethyl tetrahydrofurfuryl ether tetraliydro- 'lri h l l h t inmate) 20 p eny piosp a e A 300 Ethyl acetate 100 Ecample 16 'Jellulose acetate propionate 100 in -cH,-(oo,m).o '-cm 2o (Tetraethylene glycol tetrahydrofurfuryl ether acetate) Butyl phfim'lnh: 20 Ethyl'lactate 100 Acetone 100 Exam tile Cellulose nitrate 100 Hz-C (3H1 (Triethylene glycol tetrahydrofurfuryl ether benzyloxyacetate) Ester gum Ethyl acetat 200 Toluene 100 Efl'mnnl 100 Example 18 Cellulose butyrate 100 Hr-C CH: 7 GHQ-CH; H C n-cm-o-mm-og-cn CH: 40

O CHI-CH1 (Ethylene glycol tetrahydrofturfuryl ether tetrahydrobenzoa e years. The sum total of the above advantageous properties of a product produced from our new composition is considerably in excess of that of products produced with what have previously been regarded as the better plasticizers.

- In order that those skilled in this art may better understand our invention we would state, by

,way of illustration, that for the manufacture of photographic film or other sheets our new composition of matter may in general be compolmded as follows: 100 parts of acetone soluble cellulose acetate, 1. e. cellulose acetate containing from 38% to 42% acetyl radical, approximately is dissolved with stirring at atmospheric temperature in 300 to 500 parts, preferably 400 parts, by weight of acetone. To this solution may'be added from 5-50 parts by weight, of, any one of the above.

prasticizers, it being found preferable to employ acetate and our new plasticizers may also occur to those skilled in this art. In like manner our plas ticizers may be compounded with other single R or mixed organic esters of cellulose, such as cellulose aceto-stearate, aceto-malate, or cellulose nitro-acetate, or with the celulose ethers, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed.

Our novel plasticizer' may be employed also with advantage in connection with a number of the known lacquer and varnish formulas with Ethylene chloride 300 AW 100 which it may be found to be compatible. In such Example 19 cases the plasticizer is usually first put into solu- C b mo tion with the cellulose derivative solution and, 32% 5%, i I if non-solvents are added, only to such an extent H I H CH o c H O C C H m as will not precipitate thederivative from solution. Also the plasticizer is usually employed in larger amounts, such as from to parts, in (Penta igfi'gig compounding lacquers. Other uses within the gigg e y 8 scope of our invention will also suggest them- 1Or 3 n a 100 selves tothose skilled in the art and are to be Example 20 Parts Ethyl cellul 100 CHr-CH:

cm-o-cm-c-o-cm-cn cn-cm-ocinr-o c-cm-oc 4o 1 0 o A f (Totrahydrofurane-2-fi-hydroxyetlioxymethoxy acetate B-Omega-hydrcxy methyl methoxy acetate) 4 0 Compositions of matter prepared as above deincluded within the scope of the claims appended scribed may be deposited upon any suitable film hereto.

7 than ordinary. newsprint.

film still maintains flexibility (in contrast to" almost complete lack of flexibility where no plasticizer is used) demonstrating that the film will withstand ordinary usage satisfactorily for-many What we claim is:

1. The process of conditioning yarn to render it more amenable to textile operations including knitting, weaving, spinning and the like which comprises applying thereto a lubricating and softet or containing organic derivatives of cellulose to render it more amenable to textile operations including knitting, 'weaving, spinning and the like which commises applying'thereto a lubricating and softenlng'cornposition containing as its essential lubricatingand softening component an ester of a hyarozlfyalkoxy tetrahydrofurfuryl ether a hydroxyalkoxy tetrahydroiurfuryl ether having the formula: V

' Hto 0-3111 I 11- cH,-(oc,H.)..-on'

where n is a small whole number at least one.

4. The process of conditioning yarn composed of or containing cellulose acetate to render it more amenable to textile operations including knitting, weaving, spinning, and the like, which comprises applying thereto a lubricating and softening composition containing as its essential lubricating and softening component an ester of a hydroxyalkoxy tetrahydrofurfuryl ether having the formula:

H:-C-C-Hz H- ocH,-(0olm)..o1a

where n is a small whole number at least one, and a textile lubricant.

5. 'I'extile yarns amenable to textile operations including knitting, weaving, spinning, and the like, impregnated with a lubricant containl fl as its essential lubricating and softening component an ester of a hydroxyalkoxy tetrahydrofurturyl ether having the formulas where n is a small whole number at least one.

6. Textile yarns composed of or, containing or ganic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning and the like, impregnated with a conditioning agent comprising an ester of a hydroxyalkoxy tetrahydrofurfuryl ether having the formula:

where n is a small whole number at least one.

'7. Textile yarns composed of or containing organic derivatives of cellulose amenable to textile operations including knitting, weaving, spinning and the like, impregnated with a conditioning agent comprising an ester of a hydroxyalkoxy tetrahydrofurfuryl ether having the formula:

Where n is a small whole number at least one, and a textile lubricant.

JOSEPH B. DICKEY. JAME8 G. MCNALLY. 

